Addition of Nucleophiles to Fragment Ions in Mass Spectrometers under Electrospray-Ionization Conditions

Horni, Albert; Hesse, Manfred

doi:10.1002/(sici)1522-2675(19991110)82:11<1969::aid-hlca1969>3.0.co;2-m

Cited by 9 publications

(13 citation statements)

References 6 publications

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“…Ion‐neutral complexes are formed when ions coordinate to neutral molecules 1. The formation of such complexes by ion‐molecule reactions has previously been reported in mass spectrometry 2. Most observations on ion‐molecule adducts have been made in experiments conducted with quadrupole ion trap and Fourier transform ion cyclotron resonance mass spectrometers 3–9.…”

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confidence: 99%

“…Even aerial oxygen in an ion trap has been found to combine with negative metalloorganic fragment ions during collisional activation 10. Although less frequent, ion‐neutral adduct formation has even been observed in collision cells of triple quadrupole and quadrupole time‐of‐flight (Q‐ToF) instruments 2, 11. Ion‐molecule adducts can often be a nuisance: they complicate the interpretation of mass spectrometric data because the ‘authenticity’ of the ions is lost.…”

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confidence: 99%

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An unexpected ion‐molecule adduct in negative‐ion collision‐induced decomposition ion‐trap mass spectra of halogenated benzoic acids

Attygalle

Kharbatia

Bialecki

et al. 2006

Rapid Comm Mass Spectrometry

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The ion observed at m/z 145 when product ion spectra of iodobenzoate anions are recorded using ion-trap mass spectrometers corresponds to the adduct ion [I(H(2)O)](-). The elements of water required for the formation of this adduct do not originate from the precursor ion but from traces of moisture present in the helium buffer gas. A collision-induced decomposition (CID) spectrum recorded from the [M-H](-) ion (m/z 251) derived from 3-iodo[2,4,5,6-(2)H(4)]benzoic acid also showed an ion at m/z 145. This observation confirmed that the m/z 145 is not a product ion resulting from a direct neutral loss from the carboxylate anion. (79)Bromobenzoate anions produce similar results showing an ion at m/z 97 for [(79)Br(H(2)O)](-). The ion-molecule reaction observed here is unique to ion-trap mass spectrometers since a corresponding ion was not observed under our experimental conditions in spectra recorded with in-space tandem mass spectrometers such as triple quadrupole or quadrupole time-of-flight instruments.

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confidence: 99%

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confidence: 99%

An unexpected ion‐molecule adduct in negative‐ion collision‐induced decomposition ion‐trap mass spectra of halogenated benzoic acids

Attygalle

Kharbatia

Bialecki

et al. 2006

Rapid Comm Mass Spectrometry

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“…6−9 Although less common, ion-neutral adduct peaks have also been observed in the spectra recorded on tandem-in-space instruments when reactants such as water, 10−13 methanol, ethanol, nitrogen, 14,15 oxygen, 16 and carbon dioxide 17 are either present as impurities, or added intentionally as reagents to the collision gas. 18,19…”

Section: Introductionmentioning

confidence: 99%

Fortuitous Ion–Molecule Reaction Enables Enumeration of Metal–Hydrogen Bonds Present in Gaseous Ions

2019

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Upon mass selection and ion activation under mass spectrometric conditions, gaseous formate adducts of many metal formates undergo decarboxylation and form product ions that bear metal–hydrogen bonds. Fortuitously, we noted that negative-ion spectra of several such formate adducts showed many peaks that could not be rationalized by the conventional fragmentation pathways attributed to the precursor ion. Subsequent experimentation proved that these enigmatic peaks are due to an ion–molecule reaction that takes place between traces of adventitious water vapor in the collision gas and the in situ formed product anions bearing metal–hydrogen bonds, generated by the fragmentation of the formate adducts. Results show that metal–hydrogen bonds of the group 2 elements are particularly susceptible to this reaction. For example, in the product-ion spectrum of [Sr( η 2 - O 2 CH) 3 ] − , the peak at m / z 91 for SrH 3 – was accompanied by three peaks at higher m / z ratios. These peaks, at m / z 107, 123, and 139, represented SrH 2 (OH) 1 – , SrH 1 (OH) 2 – , and Sr(OH) 3 – , respectively. These satellite peaks, which were separated by 16 m / z units, were attributed to adducts formed due to the high affinity of gas-phase anions bearing metal–hydrogen bonds to water. Although undesired, these peaks are diagnostically useful to determine the number of metal–hydrogen bonds present in a precursor ion. Even though the peaks were less pronounced, analogous reactions were noted from the adducts of the group 1 elements as well. Moreover, Gibbs free energy values computed for the interaction of [H-Mg(η 2 -O 2 CH) 2 ] − with water to form [HO-Mg(η 2 -OCOH) 2 ] − and H 2 indicated that this is an exergonic reaction.

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“…Horni and Hesse were apparently the first to detect this phenomenon using a triple‐stage quadrupole mass spectrometer 1. They noted that the [MH − NH 3 ] + ion of 5‐amino‐1 H ‐imidazole‐4‐carboxamide at m / z 110 in Q1 was the ‘parent’ of an ion detected in Q3 at m / z 128, formulated as 5‐hydronium‐1 H ‐imidazole‐4‐carboxamide.…”

Section: Introductionmentioning

confidence: 99%

“…While the confusing nature of these addition reactions is obvious, in three of the above studies the authors pointed out the possible utility of the phenomenon in structural analysis. Thus, in addition to the aforementioned Ag + ion amino acid specificity,5 alcohols more complex than methanol were seen to provide less adduction,1, 3 emphasizing the steric requirements of such complexes, and the high abundance of the [M − CH 3 + H 2 O] + ions was suggested as being useful in the characterization of silylated fatty acids 4. In this light, we have examined the behavior of a series of sulfonated dyes and some aromatic aminosulfonic acids upon MS/MS conditions in an ion trap mass spectrometer.…”

Section: Introductionmentioning

confidence: 99%

Attachment of neutrals during tandem mass spectrometry of sulfonic acid dyes andintermediates in an ion trap

et al. 2002

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Several positional isomers of 2-(2-quinolinyl)-1H-indene-1,3(2H)-dione mono- and disulfonic acids prepared as reference materials for development of analytical methods involved in FDA certification of D&C Yellow No. 10 (Quinoline Yellow) were found consistently to show [MH + 14](+) ions when their electrospray- or atmospheric pressure chemical ionization-prepared MH(+) ions were subjected to collisional activation. The source of these ions was found to be the methanol used as solvent in these procedures which combined with their [MH - H(2)O](+) ions under chemical ionization conditions. The reaction was found to be sensitive to their isomeric and chemical structures and other examples of this process are reviewed.

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Addition of Nucleophiles to Fragment Ions in Mass Spectrometers under Electrospray-Ionization Conditions

Cited by 9 publications

References 6 publications

An unexpected ion‐molecule adduct in negative‐ion collision‐induced decomposition ion‐trap mass spectra of halogenated benzoic acids

An unexpected ion‐molecule adduct in negative‐ion collision‐induced decomposition ion‐trap mass spectra of halogenated benzoic acids

Fortuitous Ion–Molecule Reaction Enables Enumeration of Metal–Hydrogen Bonds Present in Gaseous Ions

Attachment of neutrals during tandem mass spectrometry of sulfonic acid dyes andintermediates in an ion trap

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